This invention relates to certain novel silanes and to the synthesis of silylated and N-silylated organic compounds therewith.
Typical procedures for the synthesis of silylated and N-silylated bis and mono(cyclopentadienyl) and indenyl ligands involve the addition of Cl2Si(CH3)2 during synthesis of monocyclopentadienyl compounds to the lithiated ligand precursor. These procedures are not cost effective due to a requirement for excess Cl2Si(CH3)2, the production of undesirable by-products, and a consequent need for expensive purification procedures.
In this specification, the following expressions have the meanings set forth:
1. MsO means CH3O3S or 
2. MsOH means CH4O3S or 
3. TfO means CF3O3S or 
4. TfOH means CHF3O3S or 
5. Monocyclopentadienyl ligand means any ligand having the formulae C5HXRy, wherein:
X=0-5
y=0-5
R=any alkyl or aromatic group or combination thereof, and H or R can occupy any one or more of the positions 1 to 5 of the formula 
For example, R may be an alkyl group having one to eight carbon atoms including but not limited to methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, hexyl or octyl. Methyl is the preferred alkyl group. R, when an aromatic group, may be phenyl, xylyl, mesityl, naphthyl or fluorenyl.
6. Silylated monocyclopentadienyl ligand means any ligand having the formula (R3Si)ZC5HXRy, wherein C5HXRy is as defined in definition 5, Z=1-5 and R and Ry are identical or different alkyl or aromatic groups.
7. N-silylated monocyclopentadienyl ligand means any ligand having the formula RNH(SiR2)C5HXRy, wherein C5HXRy is as defined in definition 5, and R and Ry are identical or different alkyl or aromatic groups.
8. Silylated biscyclopentadienyl ligand means any ligand having the formula (C5HXRy)2SiR2, wherein C5HXRy and Ry are as defined by definitions 6 and 7.
9. Silylated monoindenyl ligand means any ligand having the formula (R3Si) (C9HXRy) wherein
X=0-7
y=0-7
H or R can occupy any positions 1 to 7 and R3Si can occupy only position 3 of the formula 
wherein R and Ry are as defined by definitions 6 and 7.
10. N-silylated monoindenyl ligand means any ligand having the formula RNH(SiR2)C9HXRy, wherein R and Ry are as defined by definitions 6 and 7. (C9HXRy) is as defined in definition 9 and wherein X=0-7 and y=0-7.
11. Silylated bisindenyl ligand means any ligand having the formula (R2Si)C9HXRy wherein R and Ry are as defined in definitions 6 and 7; X=0-7 and y=0-7.
One aspect of the invention includes novel silanes having the Formula (I):
(CX3SO3)2SiR2xe2x80x83xe2x80x83(I)
or the Formula (II): 
in which X is H or F, each R in formula (I) may be the same or a different alkyl or aromatic group as defined by definition 5 with the proviso that when X is F in formula (I), R is not methyl, and R1 is an alkyl or aromatic group which may be the same or different from R.
Another aspect of the invention is a method for the synthesis of silylated and N-silylated compounds having the Formula (III)
xe2x80x83Y2Si(R)2xe2x80x83xe2x80x83(III)
or the Formula (IV) 
in which Y is any organic group and in which R and R1 are the same or different organic groups, preferably substituted or unsubstituted aliphatic or aryl groups as defined by definition 5.
The invention includes methods for reacting organic alkali metallides having the formula YM, in which Y is any organic group and M is any alkali metal with a silane having the Formula (I) or Formula (II) wherein the product is a compound having the Formula (III) or Formula (IV).
A first step of such methods includes preparation of an organic alkali metallide. Methods for the preparation of such compounds are known. For example, any compound having a xe2x80x94CH group, preferably acidic, is reacted with an alkali metal alkyl having the formula R3M, in which R3 may be any hydrocarbyl group and M may be lithium, potassium or sodium. M may also be a magnesium halide. N-butyl lithium or tert-butyl lithium are preferred RM compounds. The reaction is conducted in a non-interfering solvent, preferably diethyl ether or tetrahydrofuran, which may also include or be combined or mixed with a hydrocarbon such as toluene. The reaction mixture contains a desired alkali metallide.
In a second step, the alkali metallide product of the first step is optionally but not necessarily isolated from the first step reaction mixture and reacted with a silane having the Formula (I) or the Formula (II). Methods for such isolating such compounds are known.
In one aspect of the invention, the compound having xe2x80x94CH group is a C5-ring containing compound useful as an olefin polymerization catalyst ligand or as a precursor of such a ligand. Such ligands include but are not limited to substituted, unsubstituted, mono-, or bis- cyclopentadienyl, indenyl, naphthenyl and antracenyl ligands. These ligands may be hydrogenated. For example, such ligands include cyclopentadienes, bis-cyclopentadienes, indenes, bis-indenes, mono- and poly- alkyl, preferably methyl, substituted cyclopentadienes and indenes, such as tetraethyl cyclopentadiene and 2-methyl indene, 2-methyl-benzo(indene), bis-2-methyl-benzo(indene), dimethyl silane, substituted, unsubstituted and bis-phenanthrene, and cyclopentaphenanthrene which may be but need not be hydrogenated.
Another aspect of the invention may include a method which comprises combining a compound having the formula Q1-(Z)-Q2Li2 and a compound having the formula R13SiO3R2in a non-interfering solvent wherein said compound having the formula Q1-(Z)-Q2Li reacts with the compound having the formula R13SiO3R2 to produce a compound having the formula
R13SiQ1(Z)xQ2SiR13
or
R13SiQ1 where Q1=indene
or
R13SiQ2 where Q2=cyclopentadiene
wherein R1 and Q1 and Q2 each have 1 to 10 carbon atoms are the same or different aryl, preferably phenyl, and R2 are identical or different alkyl groups.
Specifically, Q1 and Q2 
(i) may be the same or different;
(ii) are preferably unsubstituted;
(iii) may be substituted at any position not occupied by linkage to (Z)x or to lithium and
(iv) Z is a linking group, preferably (CH2)y in which y is 1 to 6 or Si(R2) wherein R2 is a 1 to 6 carbon atom alkyl group.
Useful Q1 and Q2 substituents include one to six carbon atom alkyl, preferably methyl, groups; halogens, preferably chorine, fluorine or bromine, and substituents which form rings with two Q1 or Q2 carbon atoms.
Compounds having the formula Q1(Z) Q2Li are prepared in known manner by reacting a compound of formula Q1(Z)x Q2 with an alkyl lithium compound, preferably n-butyl or t-butyl lithium in a non-interfering solvent, preferably ether or tetrahydrofuran. The lithiation reaction is appropriately conducted at a temperature of from about xe2x88x9280xc2x0 C. to about 40xc2x0 C.
The reaction mixture which contains lithiated Q1-(X)x Q2 may be combined directly with R13SiO3SR2 to yield R13SiQ1(X)x Q2SiR3. The reaction proceeds to substantial completion in about thirty minutes at room temperature. See Example 8. Alternatively, the lithium salt may be isolated prior to reaction with R13SiO3SR2.
The Formula (I) silanes may be prepared by reacting a compound of the formula R1SO3H, in which R1 is any straight or branched chain alkyl group preferably having one to eight carbon atoms, with a compound of the formula X2SiQ2, in which X and Q are as defined.
The synthesis of one Formula (I) silane is illustrated by Equation 1:
RT=Room Temperature.
The novel Formula (II) silanes are synthesized by reacting RSO3H with a compound having the formula (YNH)2SiQ2, in which R and Q are as defined, and Y is an alkyl group which may be the same as or different from Q. See Equation 2: 